Synthesis of ultrasmall cerium oxide nanoparticles in deep eutectic solvent and their application in an electrochemical sensor to detect dopamine in biological fluid.

A solvothermal synthesis of ultrasmall cerium oxide nanoparticles (USCeOxNPs) with an average size of 0.73 ± 0.07 nm using deep eutectic solvent (DES) as a stabilizing medium at a temperature of 90 ºC is reported. Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were used to morphologically characterize the USCeOxNPs. These revealed approximately spherical shapes with emission lines characteristic of cerium. Selected area electron diffraction (SAED) was used to determine the crystalline structure of the cerium oxide nanoparticles (CeO2NPs), revealing the presence of crystalline cubic structures. The USCeOxNPs-DES/CB film was characterized by scanning electron microscopy (SEM), which demonstrated the spherical characteristic of CB with layers slightly covered by DES residues. DES was characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR), indicating its formation through hydrogen bonds between the precursors. An electrochemical sensor for dopamine (DA) determination in biological fluids was developed using the USCeOxNPs together with carbon black (CB). An enhanced current response was observed on DA voltammetric determination, and this can be attributed to the USCeOxNPs. This sensor displayed linear responses for DA in the range 5.0 × 10-7 mol L-1 to 3.2 × 10-4 mol L-1, with a limit of detection of 80 nmol L-1. Besides detectability, excellent performances were verified for repeatability and anti-interference. The sensor based on USCeOxNPs synthesized in DES in a simpler and environmentally friendly way was successfully applied to determine DA in biological matrix.

Cerium oxide nanoparticles: Chemical properties, biological effects and potential therapeutic opportunities (Review).

The chemistry of pure cerium oxide (CeO2-x) nanoparticles has been widely studied since the 1970s, especially for chemical catalysis. CeO2-x nanoparticles have been included in an important class of industrial metal oxide nanoparticles and have been attributed a range of wide applications, such as ultraviolet absorbers, gas sensors, polishing agents, cosmetics, consumer products, high-tech devices and fuel cell conductors. Despite these early applications in the field of chemistry, the biological effects of CeO2-x nanoparticles were only explored in the 2000s. Since then, CeO2-x nanoparticles have gained a spot in research related to various diseases, especially the ones in which oxidative stress plays a part. Due to an innate oxidation state variation on their surface, CeO2-x nanoparticles have exhibited redox activities in diseases, such as cancer, acting either as an oxidizing agent, or as an antioxidant. In biological models, CeO2-x nanoparticles have been shown to modulate cancer cell viability and, more recently, cell death pathways. However, a deeper understanding on how the chemical structure of CeO2-x nanoparticles (including nanoparticle size, shape, suspension, agglomeration in the medium used, pH of the medium, type of synthesis and crystallite size) influences the cellular effects observed remains to be elucidated. In the present review, the chemistry of CeO2-x nanoparticles and their impact on biological models and modulation of cell signalling, particularly focusing on oxidative and cell death pathways, were investigated. The deeper understanding of the chemical activity of CeO2-x nanoparticles may provide the rationale for further biomedical applications towards disease treatment and drug delivery purposes.

Cerium oxide-doped PEDOT nanocomposite for label-free electrochemical immunosensing of anti-p53 autoantibodies.

A label-free nanoimmunosensor is reported based on p53/CeO2/PEDOT nanobiocomposite-decorated screen-printed gold electrodes (SPAuE) for the electrochemical detection of anti-p53 autoantibodies. CeO2 nanoparticles (NPs) were synthesized and stabilized with cyanopropyltriethoxysilane by a soft chemistry method. The nanoimmunosensing architecture was prepared by in situ electropolymerization of 3,4-ethylenedioxythiophene (EDOT) on SPAuE in the presence of CeO2 NPs. The CeO2 NPs and Ce/PEDOT/SPAuE were characterized by scanning and transmission electron microscopy, dynamic and electrophoretic light scattering, ultraviolet-visible spectrophotometry, X-ray diffraction, Fourier-transform infrared spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Ce/PEDOT/SPAuE was biofunctionalized with p53 antigen by covalent bonding for the label-free determination of anti-p53 autoantibodies by differential pulse voltammetry. The nanobiocomposite-based nanoimmunosensor detected anti-p53 autoantibodies in a linear range from 10 to 1000 pg mL-1, with a limit of detection (LOD) of 3.2 pg mL-1. The nanoimmunosensor offered high specificity, selectivity, and long-term storage stability with great potential to detect anti-p53 autoantibodies in serum samples. Overall, incorporating organo-functional nanoparticles into polymeric matrices can provide a simple-to-assemble, rapid, and ultrasensitive approach for on-site screening of anti-p53 autoantibodies and other disease-related biomarkers with low sample volumes.

Cerium oxide nanoparticle conjugation to microRNA-146a mechanism of correction for impaired diabetic wound healing.

Diabetic wounds represent a significant healthcare burden and are characterized by impaired wound healing due to increased oxidative stress and persistent inflammation. We have shown that CNP-miR146a synthesized by the conjugation of cerium oxide nanoparticles (CNP) to microRNA (miR)-146a improves diabetic wound healing. CNP are divalent metal oxides that act as free radical scavenger, while miR146a inhibits the pro-inflammatory NFκB pathway, so CNP-miR146a has a synergistic role in modulating both oxidative stress and inflammation. In this study, we define the mechanism(s) by which CNP-miR146a improves diabetic wound healing by examining immunohistochemical and gene expression analysis of markers of inflammation, oxidative stress, fibrosis, and angiogenesis. We have found that intradermal injection of CNP-miR146a increases wound collagen, enhances angiogenesis, and lowers inflammation and oxidative stress, ultimately promoting faster closure of diabetic wounds.

Engineered nanoceria modulate neutrophil oxidative response to low doses of UV-B radiation through the inhibition of reactive oxygen species production.

To avoid aging and ultraviolet mediated skin disease the cell repair machinery must work properly. Neutrophils, also known as polymorphonuclear leukocytes, are the first and most abundant cell types which infiltrate sites of irradiation and play an important role in restoring the microenvironment homeostasis. However, the infiltration of neutrophils in ultraviolet-B (UV-B) irradiated skin might also contribute to the pathophysiology of skin disease. The polymorphonuclear leukocytes activation induced by UV-B exposure may lead to prolonged, sustained NADPH oxidase activation followed by an increase in reactive oxygen species (ROS) production. Our previous work showed that cerium oxide nanoparticles can protect L929 fibroblasts from ultraviolet-B induced damage. Herein, we further our investigation of engineered cerium oxide nanoparticles (CNP) in conferring radiation protection specifically in modulation of neutrophils' oxidative response under low dose of UV-B radiation. Our data showed that even low doses of UV-B radiation activate neutrophils' oxidative response and that the antioxidant, ROS-sensitive redox activities of engineered CNPs are able to inhibit the effects of NADPH oxidase activation while conferring catalase and superoxide dismutase mimetic activity. Further, our investigations revealed similar levels of total ROS scavenging for both CNP formulations, despite substantial differences in cerium redox states and specific enzyme-mimetic reaction activity. We therefore determine that CNP activity in mitigating the effects of neutrophils' oxidative response, through the decrease of ROS and of cell damage such as chromatin condensation, suggests potential utility as a radio-protectant/therapeutic against UV-B damage.

Antioxidative photochemoprotector effects of cerium oxide nanoparticles on UVB irradiated fibroblast cells.

The Ultraviolet-B radiation (UVB) might induce cellular redox imbalance which plays an important role in the development of skin disorders. Thus, the search for photochemoprotective alternatives with antioxidant efficacy would be a safe aspect towards prevention of skin diseases. Cerium oxide nanoparticles (CNPs) have antioxidant properties, that are mostly related to CNPs catalase and superoxide dismutase (SOD)-like antioxidative mimetic activity. Considering that, we investigated whether CNPs induce photochemoprotection against UVB-induced cellular damages on L929 fibroblasts. Our results showed that CNPs prevented UVB mediated L929 cell oxidative damage by reestablishing the oxidative balance through ameliorating the reactive oxygen species (ROS) level and enhancing the antioxidant enzyme activities.

Fabrication of Sputtered Ce/La, La/Ce Oxide Bilayers on AA6061 and AA7075 Aluminum Alloys for the Development of Corrosion Protective Coatings.

This work provides a comparative study on the corrosion protection efficiency of Ce, La films as well as Ce/La and La/Ce oxide bilayered coatings deposited onto AA7075 and AA6061 substrates by the radio frequency (RF) magnetron sputtering technique. The coating thickness ranged approximately from 12 to 835 nm, which changed with the deposition parameters and substrate composition. The relationship between microstructure, roughness and electrochemical performance is examined. The reactivity and crystallinity of rare earth (RE) films can be tailored by adjusting the sputtering parameters. Sputtered La films with thickness ca. 390 nm and average roughness of 66 nm showed the best corrosion protection properties in chloride medium as determined by potentiodynamic curves and electrochemical impedance spectroscopy (EIS). The method to obtain RE bilayered coatings, i.e., La/Ce or Ce/La as well as the substrate composition and applied power conditioned their inhibition properties. The RE bilayered coatings displayed better barrier properties than Ce films, which were poorer than those featured by La films.

Detection of DNA Damage Induced by Cerium Dioxide Nanoparticles: From Models to Molecular Mechanism Activated.

This chapter will present an original effort to summarize the relevant data about the cyto-genotoxicity induced by cerium dioxide nanoparticles (nanoceria) in physiologically (in vivo and in vitro) relevant models. In this way, this chapter should be extremely useful to everyone who wants to plan their research and publishing their results. Massive application of nanoceria at different fields is increasing year after year, and it is urgent to address and discuss their use and its safety-related issues. Specifically, the nanoceria are being designed for nanomedicine, cosmetics, polishing materials and additives for automotive fuels. Their unique properties include the ability to absorb UV radiation, antioxidant potential and the rapid exchange of valence between Ce4+ and Ce3+ ions associated to oxygen storage. In this chapter, the state of the art regarding the physicochemical properties of nanoceria, nanogenotoxicity detected by in vitro and in vivo systems and the general aspects in the cyto-genotoxic mechanism of nanoceria are summarized. The cyto-genotoxicity will be discussed in terms of evaluations by Comet assay, Micronucleus test, DNA damage response and oxidative stress detected in cell culture systems and in vivo test. We also described the dose dependent cyto-genotoxic effects of nanoceria based on their physical-chemical nature. Paradoxically, these particles have been characterized as either pro-oxidant or anti-oxidant in dependence of microenvironment and physiological conditions such as pH. Finally, this chapter will contribute to point out aspects of the development of new in vitro and in vivo methodologies to detect cyto-genotoxic effects of the nanoceria.

Intensification of Electrochemical Performance of AA7075 Aluminum Alloys Using Rare Earth Functionalized Water-Based Polymer Coatings.

This work reports the effect of different amounts of ceria nanoparticles on UV resistance and barrier properties of water-based polyurethane (WPU) on glass and AA7075 aluminum alloy substrates. Hybrid coatings were synthesized from an aliphatic WPU⁻HDI (1,6-hexamethylene di-isocyanate) and cerium oxide nanoparticles (CeO2) with an average particle size distribution of about 25 nm. Different nanoceria amounts (1, 3 and 5 wt %), mixing times (30, 60 and 120 min) and methods to disperse the nanostructures into the polymer matrix (magnetic stirring and sonication) were evaluated. Initially, the dispersion of CeO2 nanoparticles embedded in the polymer matrix and displacement in the corrosion potential (Ecorr) were analyzed by confocal scanning laser microscopy (CLSM) and open circuit potential (Eocp) measurements. According to this behavior, the dispersion and water ratio required during the polymerization process were established. Coated samples obtained after the second stage were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and optical light microscopy. In addition, optical measurements on glass substrates were evaluated with UV-vis spectroscopy. The effect of the synthesis parameters on the corrosion behavior of WPU⁻CeO2/AA7075 systems was investigated with Eocp and electrochemical impedance spectroscopy (EIS) in a 3 wt % NaCl solution. In addition, the films were subjected to 180 h of accelerated weathering. The results show that the combination of specific nanoceria addition with the optimal synthesis parameters enhances optical transparence of WPU as well as barrier properties. From these, the coated specimens prepared with 3 wt % of ceria content and sonicated for 30 min showed a highly dispersed system, which results in a high charge transfer resistance. The observed properties in clear coats deposited on metallic substrates suggested an improvement in the appearance and less deterioration in UV exposure in comparison with pure WPU, enhancing the protective properties of the AA7075 aluminum alloy when exposed to a corrosive medium.

Catalysts with Cerium in a Membrane Reactor for the Removal of Formaldehyde Pollutant from Water Effluents.

We report the synthesis of cerium oxide, cobalt oxide, mixed cerium, and cobalt oxides and a Ce-Co/Al2O3 membrane, which are employed as catalysts for the catalytic wet oxidation (CWO) reaction process and the removal of formaldehyde from industrial effluents. Formaldehyde is present in numerous waste streams from the chemical industry in a concentration low enough to make its recovery not economically justified but high enough to create an environmental hazard. Common biological degradation methods do not work for formaldehyde, a highly toxic but refractory, low biodegradability substance. The CWO reaction is a recent, promising alternative that also permits much lower temperature and pressure conditions than other oxidation processes, resulting in economic benefits. The CWO reaction employing Ce- and Co-containing catalysts was carried out inside a slurry batch reactor and a membrane reactor. Experimental results are reported. Next, a mixed Ce-Co oxide film was supported on an γ-alumina membrane used in a catalytic membrane reactor to compare formaldehyde removal between both types of systems. Catalytic materials with cerium and with a relatively large amount of cerium favored the transformation of formaldehyde. Cerium was present as cerianite in the catalytic materials, as indicated by X-ray diffraction patterns.